CN103449419B - Preparation method of nitrogen-doped graphene with ultrahigh lithium storage capacity - Google Patents
Preparation method of nitrogen-doped graphene with ultrahigh lithium storage capacity Download PDFInfo
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Abstract
The invention relates to a preparation method of nitrogen-doped graphene with ultrahigh lithium storage capacity. The preparation method comprises the following steps of: A, introducing a nitrogen source during preparing graphene oxide to obtain nitrogen-doped graphene oxide; B, performing hydro-thermal treatment on nitrogen-doped graphene oxide at 180 to 200 DEG C to obtain nitrogen-doped graphene. The preparation method is high in controllability, high in repeatability, and suitable for mass production; the prepared material can be directly put into use, so that the traditional process of doping nitrogen in post-treatment is saved; the preparation method is relatively simple.
Description
Technical field
The present invention relates to the preparation field of Graphene, be specifically related to a kind of method preparing nitrogen-doped graphene from the reduction of N doping graphene oxide hydrothermal method.
Background technology
Graphene is paid close attention to widely because the specific surface area of its super large, high heat-conductivity conducting and strong Young's modulus have obtained in a lot of fields.Particularly in field of lithium ion battery, Graphene is combined with other materials, as metal oxide, metallic sulfide etc., has achieved excellent electric property.Graphene provides efficient conductive network, and the material of its load is had higher stability, thus graphene-based composite material exhibits is gone out higher lithium storage content and cyclical stability.
At present, about the doping of Graphene have also been obtained the large quantity research of people.Hotchpotch has boron, nitrogen, gas, metal and organic molecule etc., and the Graphene chemically reactive after doping and electrical property aspect obtain larger raising.Among numerous doping, nitrogen-doped graphene obtains maximum concerns, and compared to unadulterated Graphene, nitrogen-doped graphene has more active region, is so more conducive to the generation of the embedding lithium/de-lithium on its surface.In field of lithium ion battery, the graphene oxide of reduction is used as the modal substrate of matrix material, but weak inductive limits its application as conductive network, and the nitrogen-atoms in nitrogen-doped graphene can improve electroconductibility by providing more cloud density.But in report, the way of nitrogen-doped graphene is all comparatively complicated at present, all will have the process of nitrating, no matter is used alone or all makes step complicated with other material compounds.
Journal of Materials Chemistry2011,21 (14), 5430 disclose the process that a kind of atmosphere furnace heat treating process prepares nitrogen-doped graphene, thermal treatment 2 hours under 800 DEG C of ammonia atmospheres, the doping of nitrogen-atoms is made to reach 2%, nitrogen-doped graphene prepared by the method is when charging and discharging currents density is 42mA/g, and process capacity reaches 900mAh/g.
ACS Nano2011,5,5463 disclose the process that a kind of atmosphere furnace heat treating process prepares nitrogen-doped graphene, the method is by graphene oxide thermal treatment 2 hours under 600 DEG C of ammonia atmospheres, the nitrogen-doped graphene obtained circulates through 30 times under the current density of 50mA/g, capacity reaches 872mAh/g, considerably beyond the 638mAh/g capacity of non-doped graphene.
CN102120572B discloses a kind of preparation method of nitrogen-doped graphene, the Graphene of titanium oxide and trimeric cyanamide mixed grinding are placed in airtight rare gas element the high-temperature hot of carrying out calorified at 700 ~ 1200 DEG C and reduce and the obtained nitrogen-doped graphene of N doping reaction by it, and this method treatment temp is high.Again, CN102167310B discloses a kind of method of preparing nitrogen-doped graphene material with hydrothermal process: be dissolved in by graphene oxide in solvent, mix after adding tensio-active agent, then after adding nitrogenous compound again at 100 ~ 190 DEG C hydro-thermal reaction obtain nitrogen-doped graphene.This method needs tensio-active agent, and the dispersion needs of graphene oxide carry out complicated ultrasonic disperse or heated and stirred method is carried out.
Summary of the invention
In the face of existing N-doping technology Problems existing, the present inventor obtains N doping graphene oxide as presoma in this proposition by introducing nitrogenous source in the process preparing graphene oxide, then prepares nitrogen-doped graphene material by Direct Hydrothermal reduction.Like this, eliminate traditional aftertreatment nitrating process, technique is more simple, applies more extensive, only the method process of traditional redox graphene of the N doping graphene oxide in the present invention can need be obtained nitrogen-doped graphene material.
At this, first the present invention provides a kind of preparation method with the nitrogen-doped graphene of superelevation lithium storage content, comprising:
Steps A: introduce nitrogenous source in the process preparing graphene oxide, obtained N doping graphene oxide; And
Step B: obtain described nitrogen-doped graphene in N doping graphene oxide described in 180 ~ 200 DEG C of hydrothermal treatment consists.
Preparation method of the present invention is by introducing nitrogenous source in traditional preparing in the step of graphene oxide, thus obtained N doping graphene oxide, and its high temperature hydro-thermal is obtained nitrogen-doped graphene material.Compared with prior art, controllability of the present invention is high, reproducible, is applicable to scale production, and obtained material can directly be applied, and eliminates traditional aftertreatment nitrating process, makes preparation method relatively simple.
Preferably, described steps A comprises: mix described Graphite Powder 99, potassium permanganate, SODIUMNITRATE and the vitriol oil, then adds described nitrogenous source wherein, carries out first stage reaction 12 ~ 36 hours at 30 ~ 40 DEG C, be warming up to 80 ~ 90 DEG C again, carry out subordinate phase reaction 0.5 ~ 2 hour.
Preferably, in described steps A, the ratio of described Graphite Powder 99, potassium permanganate, SODIUMNITRATE and the vitriol oil can be (1g): (3g): (0.5-1g): (46-50mL).
Preferably, in described steps A, can first Graphite Powder 99 and SODIUMNITRATE be joined in the vitriol oil, then add potassium permanganate in batches.
Preferably, in described steps A, potassium permanganate can be added at 0 ~ 4 DEG C.
Preferably, in described steps A, described nitrogenous source can be added at 0 ~ 4 DEG C.
Preferably, in described steps A, add water after being warming up to 80 ~ 90 DEG C and carry out described subordinate phase reaction again, the water wherein added and the volume ratio of the vitriol oil are 2:1.
Preferably, in described steps A, add after the reaction of described subordinate phase terminates concentration be 30% hydrogen peroxide terminate reaction, the hydrogen peroxide added and the volume ratio of the vitriol oil are 2:1.
Preferably, described nitrogenous source can be trimeric cyanamide and/or urea.
Preferably, the time of described hydro-thermal reaction can be 4 ~ 8 hours.
Accompanying drawing explanation
Fig. 1 illustrates the XRD figure of nitrogen-doped graphene (embodiment 1) prepared by the present invention's example and presoma (comparative example 1) thereof;
Fig. 2 illustrates the TEM figure of nitrogen-doped graphene prepared by the present invention's example;
Fig. 3 illustrates the XPS spectrum figure of nitrogen-doped graphene prepared by the present invention's example;
Fig. 4 illustrates the C1s electronics XPS spectrum figure of nitrogen-doped graphene prepared by the present invention's example;
Fig. 5 illustrates the N1s electronics XPS spectrum figure of nitrogen-doped graphene prepared by the present invention's example;
Fig. 6 illustrates the impedance spectrogram of one embodiment of the invention 1, comparative example 2;
Fig. 7 illustrates the CV graphic representation of nitrogen-doped graphene prepared by the present invention's example;
Fig. 8 illustrates the voltage-specific storage sectional view of nitrogen-doped graphene prepared by the present invention's example;
Fig. 9 illustrates the low range circulation volume figure of one embodiment of the invention 1, comparative example 2;
Figure 10 illustrates many circulation capacity plan of one embodiment of the invention 1, comparative example 2.
Embodiment
Further illustrate the present invention below in conjunction with accompanying drawing and following embodiment, should be understood that following embodiment and/or accompanying drawing are only for illustration of the present invention, and unrestricted the present invention.
The present invention adopts trimeric cyanamide as nitrogenous source, adopts to prepare in graphene oxide at common chemical method to introduce nitrating step and prepare presoma, after high temperature hydro-thermal, obtain nitrogen-doped graphene.After the nitrogen-doped graphene of preparation is mixed with conductive agent, binding agent, spread upon on copper foil of affluxion body, assemble as lithium ion button shape cell material after then breaking into disc-shaped with mould.The present invention utilizes nitrogen-doped graphene electroconductibility high, and the feature that avtive spot is many and storage lithium ability is strong, prepares the lithium ion battery electrode material of Large Copacity, high cycle life.
The following describes step of the present invention:
(1) Graphite Powder 99, SODIUMNITRATE, the vitriol oil are stirred under ice-water bath, potassium permanganate can be added in the middle of stirring, stir and add trimeric cyanamide after 2-4 hour, middle temperature 30-40 DEG C of reaction 12-36 hour, then add hot water and carry out pyroreaction 0.5-2 hour, temperature remains on 80-90 DEG C, adds hydrogen peroxide and terminate reaction after pyroreaction is complete.Although adopt trimeric cyanamide as nitrogenous source here, should understand and can adopt other suitable nitrogenous source, such as urea.
The amount ratio of preferred Graphite Powder 99, SODIUMNITRATE, potassium permanganate and the vitriol oil can be (1g): (0.5g): (3g): (50mL), and the consumption strengthening potassium permanganate and the vitriol oil in reaction can make the degree of oxidation of graphene oxide increase.
Preferably, reaction starts preferably to use ice-water bath most, or cooling bath water temperature is below 4 DEG C, and the reaction times is 2 hours.
Preferably, potassium permanganate add best proceed step by step, within the time of ice-water bath, add a potassium permanganate every half an hour.Nitrogenous source can add with last potassium permanganate.
Preferably, the temperature of middle temperature reaction is at 30-40 DEG C, and the too low formation with graphene oxide of peeling off being unfavorable for graphite linings of temperature, temperature is too high, and graphene oxide defect is increased, and not easily forms large stretch of graphene oxide lamella.
Preferably, after middle temperature reaction terminates, the hot water added and the volume ratio of the vitriol oil are 2:1.In order to terminate pyroreaction, the concentration of the hydrogen peroxide added can be 30%, and the amount added and the volume ratio of the vitriol oil are 2:1.
(2) after reaction terminates, be cooled to room temperature, by products therefrom successively through centrifugal, filter, washing, ethanol is washed, three times repeatedly, and finally dry and obtain presoma, presoma is N doping graphene oxide through XRD, XPS analysis herein.
(3) by presoma through high temperature hydro-thermal, such as hydro-thermal 4-8 hour at 180-200 DEG C, can obtain nitrogen-doped graphene material.
Being mixed with conductive agent, binding agent by prepared nitrogen-doped graphene powder spreads upon on copper foil of affluxion body, and utilize mould to break into sheet and be encapsulated in lithium ion button shape cell and study its chemical property, concrete operations are as follows.
(1) ratio of 8:1:1 is by after nitrogen-doped graphene, conduction charcoal acetylene black, polyfluortetraethylene of binding element mixing in mass ratio, and instill a small amount of nitrogen methyl-2-pyrrolidone, grinding evenly.
(2) by the slurry uniform application that obtains on Copper Foil, and dry in 100-110 DEG C of baking oven, use belt puncher mould that Copper Foil is gone out disc-shaped electrode materials after drying.
(3) in glove box, electrode materials is encapsulated in coin shape lithium ion battery as lithium ion cell electrode.
(4) button cell is put into electrochemical workstation, adopt the method for cyclic voltammetry and constant current charge-discharge to test its chemical property.
Experiment proves that the nitrogen-doped graphene of the present invention's synthesis is used as electrode materials and has excellent chemical property, can be used for the lithium ion battery preparing large specific storage, high cycle life.
The preparation method of nitrogen-doped graphene electrode materials provided by the invention has following features:
(1) being prepared in the research in this field of its presoma N doping graphene oxide still belongs to the first time, the present invention prepares graphene oxide composite material to traditional chemical method and improves, nitrogenous source is introduced in the process of ice-water bath, compared to the method for aftertreatment graphene oxide nitrating, it is more simple that present method should use step, and a lot of aftertreatment nitrating process chemistry environmental requirement is higher, the nitrogen-doped graphene of this experiment is used then only to need gentle hydro-thermal to prepare material.
(2) mixing of nitrogen-atoms introduces higher cloud density, thus compared to unadulterated Graphene, the nitrogen-doped graphene in the present invention has higher electroconductibility, is more conducive to the transmission of electronics and ion.
(3) the nitrogen element in nitrogen-doped graphene makes Graphene show higher chemically reactive, thus has higher lithium storage content.
(4) impedance spectrum test shows, nitrogen-doped graphene is relative to unadulterated Graphene, and its electroconductibility about improves twice, and impedance has been reduced to 20 Ω after doping from 40 original Ω.
(5) specific storage is high, the nitrogen-doped graphene material of preparation under the current density of 37mA/g, specific storage up to 600mAh/g, far away higher than the 350mAh/g of non-doped graphene material.
(6) large current density electrical capacity is also higher, the nitrogen-doped graphene material of preparation under the current density of 744mA/g, specific storage up to 200mAh/g, far away higher than the 120mAh/g of non-doped graphene material.
(7) good cycling stability, the nitrogen-doped graphene material of preparation is after 60 circulations, and capacity remains unchanged substantially.
Exemplify embodiment below further to describe the present invention in detail.Should understand equally; following examples are only used to further illustrate the present invention; can not be interpreted as limiting the scope of the invention, some nonessential improvement that those skilled in the art's foregoing according to the present invention is made and adjustment all belong to protection scope of the present invention.The temperature of reaction that following example is concrete, time charging capacity etc. are also only examples in OK range, and namely, those skilled in the art can be done in suitable scope by explanation herein and select, and do not really want the concrete numerical value being defined in Examples below.
Embodiment 1
1.0g Graphite Powder 99 and 0.5g SODIUMNITRATE are dissolved in the 50mL vitriol oil, stir under ice-water bath, added 1g potassium permanganate every 0.5 hour, totally 3 times, last with adding 1g trimeric cyanamide.Be warmed up to 30 DEG C, stir 24 hours, be then warming up to 90 DEG C, dropwise add 46mL hot water, stir after 1 hour and stop insulation, add the hydrogen peroxide of 20mL30%.Subsequently obtained product is washed through centrifugal, filtration, washing, ethanol successively, three times repeatedly, finally dry and obtain presoma.Gained presoma is obtained nitrogen-doped graphene material in 6 hours 180 DEG C of hydro-thermals.And be made into slurry, smear, punch after be encapsulated in button lithium ion battery and test.
Fig. 1 is the XRD figure of the nitrogen-doped graphene prepared of example and presoma thereof, wherein the curve of comparative example 1 is the XRD spectra of presoma N doping graphene oxide, because N doping quantity not sufficient is to cause the change of XRD peak type, so the spectrogram observed is consistent with the graphene oxide that conventional chemical methods obtains.The XRD spectra of embodiment 1 is consistent with the XRD spectra of grapheme material.
Fig. 2 is the TEM figure of nitrogen-doped graphene prepared by example, can see that N doping graphene oxide has the significant two-dimensional layered structure of Graphene and fold clearly.
Fig. 3 is the XPS spectrum figure of nitrogen-doped graphene prepared by example, can see the characteristic peak occurring nitrogen element in the nitrogen-doped graphene prepared by the present invention clearly.
Fig. 4 is the C1s electronics XPS spectrum figure of nitrogen-doped graphene prepared by example, and in figure, the peak of carbon oxygen singly-bound appears at 298.8eV, and peak intensity is very weak, illustrates that graphene oxide obtains good reduction.
Fig. 5 is the N1s electronics XPS spectrum figure of nitrogen-doped graphene prepared by example, and the nitrogen peak in figure can be expressed as the peak position of three kinds of different chemical environment by swarming, and this is the significant three kinds of swarmings of nitrogen-doped graphene.
Fig. 6 is the impedance spectrogram of embodiment 1, comparative example 2, and as can be seen from the figure unadulterated Graphene impedance is at 40 Ω, and nitrogen-doped graphene impedance is 20 Ω, and after visible nitrating, the electroconductibility of material has increased significantly.
Fig. 7 is the CV graphic representation of nitrogen-doped graphene prepared by example, the integral area of first charge-discharge is larger, visible capacity is first higher, here irreversible lithium storage content is comprised, when second time discharge and recharge, capacity just declines to some extent, after the tenth discharge and recharge, capacity keeps stable, and the nitrogen-doped graphene material circulation stability that visible the present invention does is better.
Fig. 8 is the voltage-specific storage sectional view of nitrogen-doped graphene prepared by example, therefrom obviously can find out that the embedding lithium of nitrogen-doped graphene material takes off lithium voltage at about 0.2V.
Fig. 9 is the low range circulation volume figure of embodiment 1, comparative example 2, nitrogen-doped graphene material under the charging and discharging currents density that 37mA/g is lower, specific storage up to 600mAh/g, far away higher than the 350mAh/g of non-doped graphene material.
Figure 10 is many circulation capacity plan of embodiment 1, comparative example 2, the large current density electrical capacity of material of the present invention is also higher, preparation nitrogen-doped graphene material under the current density of 744mA/g, specific storage up to 200mAh/g, far away higher than the 120mAh/g of non-doped graphene material.
Comparative example 1
1.0g Graphite Powder 99 and 0.5g SODIUMNITRATE are dissolved in the 50mL vitriol oil, stir under ice-water bath, added 1g potassium permanganate every 0.5 hour, totally 3 times, last with adding 1g trimeric cyanamide.Be warmed up to 30 DEG C, stir 24 hours, be then warming up to 90 DEG C, dropwise add 46mL hot water, stir after 1 hour and stop insulation, add the hydrogen peroxide of 20mL30%.Subsequently obtained product is washed through centrifugal, filtration, washing, ethanol successively, three times repeatedly, finally dry and obtain presoma.This comparative example does not carry out follow-up hydro-thermal reaction, and obtained sample is N doping graphene oxide, and its XRD characterizes and sees Fig. 1, and this contrast material is to illustrate that hydrothermal method effectively can change graphene oxide into grapheme material.
Comparative example 2
1.0g Graphite Powder 99 and 0.5g SODIUMNITRATE are dissolved in the 50mL vitriol oil, stir under ice-water bath, added 1g potassium permanganate every 0.5 hour, totally 3 times.Be warmed up to 30 DEG C, stir 24 hours, be then warming up to 90 DEG C, dropwise add 46mL hot water, stir after 1 hour and stop insulation, add the hydrogen peroxide of 20mL30%.Subsequently obtained product is washed through centrifugal, filtration, washing, ethanol successively, three times repeatedly, finally dry and obtain presoma.Gained presoma is obtained nitrogen-doped graphene material in 6 hours 180 DEG C of hydro-thermals.And be made into slurry, smear, punch after be encapsulated in button lithium ion battery and test.This contrast sample does not introduce nitrogenous source, thus unadulterated grapheme material asked by the material of preparation.Can be found by the contrast of Fig. 6, its electroconductibility is weaker than nitrogen-doped graphene, can be found by the contrast of Fig. 9, Figure 10, and its lithium storage content is also far below nitrogen-doped graphene material.
Industrial applicability: the simple controlled applicable scale production of method preparation technology of the present invention, obtained nitrogen-doped graphene material has high electroconductibility, and be prepared into that specific storage after electrode materials is high, doubly forthright good, good cycling stability, be suitable for very much the electrode materials making lithium ion battery, have broad application prospects.
Claims (8)
1. there is a preparation method for the nitrogen-doped graphene of superelevation lithium storage content, it is characterized in that, comprising:
Steps A: introduce nitrogenous source in the process preparing graphene oxide, obtained N doping graphene oxide, wherein, described steps A comprises: mixing graphite powder, potassium permanganate, SODIUMNITRATE and the vitriol oil, add described nitrogenous source wherein again, first stage reaction 12 ~ 36 hours is carried out at 30 ~ 40 DEG C, be warming up to 80 ~ 90 DEG C again, carry out subordinate phase reaction 0.5 ~ 2 hour, in described steps A, the ratio of described Graphite Powder 99, potassium permanganate, SODIUMNITRATE and the vitriol oil is 1g:3g:(0.5 ~ 1g): (46 ~ 50mL); And
Step B: obtain described nitrogen-doped graphene in N doping graphene oxide described in 180 ~ 200 DEG C of hydrothermal treatment consists.
2. preparation method according to claim 1, is characterized in that, in described steps A, first joins in the vitriol oil by Graphite Powder 99 and SODIUMNITRATE, then adds potassium permanganate in batches.
3. preparation method according to claim 2, is characterized in that, in described steps A, at 0 ~ 4 DEG C, adds potassium permanganate.
4. preparation method according to claim 1, is characterized in that, in described steps A, at 0 ~ 4 DEG C, adds described nitrogenous source.
5. preparation method according to claim 1, is characterized in that, in described steps A, add water after being warming up to 80 ~ 90 DEG C and carry out described subordinate phase reaction again, the water wherein added and the volume ratio of the vitriol oil are 2:1.
6. preparation method according to claim 1, is characterized in that, in described steps A, add after the reaction of described subordinate phase terminates concentration be 30% hydrogen peroxide terminate reaction, the hydrogen peroxide added and the volume ratio of the vitriol oil are 2:1.
7. preparation method according to claim 1, is characterized in that, described nitrogenous source is trimeric cyanamide and/or urea.
8. preparation method according to claim 1, is characterized in that, the time of described hydro-thermal reaction is 4 ~ 8 hours.
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| CN103691471B (en) * | 2013-12-19 | 2016-03-30 | 南开大学 | The preparation method of nitrogen-doped graphene material |
| CN103803539B (en) * | 2014-02-17 | 2015-09-09 | 上海交通大学 | A kind of N doping graphene oxide composite material and preparation method thereof |
| CN104882608A (en) * | 2015-05-06 | 2015-09-02 | 江南大学 | Preparation method of N-doped 3D graphene/graphite lithium ion battery negative material |
| CN106189298B (en) * | 2016-08-17 | 2019-05-24 | 河南师范大学 | A kind of emulsified bitumen modifying agent and preparation method thereof |
| CN109103432B (en) * | 2018-08-22 | 2020-09-11 | 深圳市创世达实业股份有限公司 | Pyrovanadate/nitrogen-doped graphene composite material and preparation method and application thereof |
| CN114899406B (en) * | 2022-07-13 | 2022-11-22 | 中博龙辉装备集团股份有限公司 | Nitrogen-doped graphene manganese oxide nanowire composite material and preparation method and application thereof |
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